Anthraquinone vat dyestuffs



ANTHRAQUINONE VAT DYESTUFFS N Drawing. Application December 19, 1952Serial No. 327,032

Claims priority, application Switzerland December 21, 1951 6 Claims.(Cl. 260-276) According to this invention valuable new anthraquinone vatdyestuffs are made by treating with a carbazolizing agent atrianthrimide, in which the imido bridges bound to the centralanthraquinone nucleus are in the 1:4-position relatively to one anotherand in which a single anthraquinone radical in an end position containsa fused on acridone ring and the NH-group of the latter ring is inpara-position relatively to the anthrimide bridge.

As will be understood from the foregoing definition, the trianthrimidesserving as starting materials in the present process contain thestructure of the constitution The ring fused on the heterocyclic ringmay, for example, be a naphthalene ring or especially a benzene ring,and these rings may contain substituents of the kind usual in vatdyestuffs, for example, halogen atoms such as chlorine, methoxy groupsor phenyl or phenoxy radicals. The anthraquinone nuclei may also containsubstituents, and substituents of the aforesaid kind may advantageouslybe present in the central anthraquinone nucleus 5 and/or in the endanthraquinone radical to which the acridone ring is not fused. Thus, forexample, the aforesaid end anthraquinone radical may contain in anOL-POSltion, for example, in the 4- or S-position relatively to theanthrimide bridge an acylamino group, if desired, a henzoylamino groupin which the benzene radical is substituted or unsubstituted, and thecentral anthraquinone nucleus may contain ahalogen atom or atoms, suchas chlorine as substituents in one or both of the fl-positions of the6-membered ring not bound to the anthrimide 55 bridges. Especiallyadvantageous results are obtained, for example with trianthrimides whichare free from substituents in the anthraquinone nuclei. 7

Such trianthrimides can be obtained with advantage by the reaction of4-halogen-l:l'-dianthrimides with 4- aminoanthraquinone-2:1(N)-benzornaphthacridones.

As carbazolizing agents there may be used, for example, mixturescontaining titanium tetrachloride or aluminum chloride, for example,mixture or loose addition compounds of aluminum chloride with sodiumchloride Patented June 3, 195% are carbazoles which contain a singleacridone ring and correspond to the formula in which R R and R representanthraquinone radicals, and R represents an aromatic radical fused on tothe heterocyclic ring in the manner indicated, and in which the NHgroups bound to the anthraquinone radicals R and R are in 1:4-positionrelatively to one another and the anthraquinone radical R is bound inOt-POSltlOIl to the -NH group.

These vat dyestuffs are distinguished by producingvaluable tints, forexample, within the range of green to olive, and also by producingdyeings having a good fastness to light, chlorine and bucking. They canbe used in known manner as pigments or for dyeing or printing (forexample, by the so-called potash process) a very wide variety ofmaterials, for example, cotton, linen, artificial silk or staple fibersof regenerated cellulose, and other' cellulose fibers, and also silk,wool, wholly synthetic fibers such as those of superpolyamides orsuperpolyurethane. Furthermore, the new dyestuffs can also be convertedby methods in themselves known into leuco preparations, especiallysulfuric acid ester salts, and used for dyeing or printing by methodsknown for this class of dyestuffs.

The following examples illustrate the invention, the parts andpercentages being by weight unless otherwise stated, and therelationship of parts by weight to parts by volume being the same asthat of the kilogram to the liter:

Example 1 15.4 parts of 4-chloro-1:1-dianthrimide, 11.35 parts of4-aminoanthraquinone-2:'1(N)-benzacridone, 5 parts of sodium carbonate,0.5 parts of cuprous chloride and 250 parts of nitrobenzene are finelyground at room temperature, and then heated while stirring andmaintained at 210 C. for 10 hours. After cooling, the condensationproduct is separated by filtering with suction, and the residue istreated with steam.

The aqueous suspension of: the product free from nitrobenzene isacidified with hydrochloric acid, filtered'with suction, and the filterresidue washed V The condensation product is a dark powder whichdissolves in concentrated sulfuric acid with an olive-black coloration.

100 parts of aluminum chloride are introduce at 10- C. into 200 parts ofanhydrous pyridine, while stirring. The mixture is heated up to C., andat that temperature 20 parts of condensation product obtained asdescribed in the preceding paragraph are added. In the course of 45minutes the temperature is raised to 139 141 C. with the simultaneousdistillation of pyridine. The whole is stirred for one hour at 140 C.,and there action mixture is poured'into 3000 'parts' of'cold water."

neutral and dried.

To the suspension are added 400 parts of sodium hydroxide solution of 30percent strength and 100 parts of sodium hypochlorite solutioncontaining about 10 percent of active chlorine. The mixture is heated to90 C., filtered with suction, and the filter residue is washed neutraland dried. The dyestuff is a dark powder which dissolves in concentratedsulfuric acid with a dirty violet coloration and dyes cotton from ayellow-brown vat fast black-olive tints.

Example 2 4.65 parts of 4-chloro-1:1-dianthrirnide, 4.1 parts of 4amino-3:5'-dichloro 2:1(N) 1':2(N)-anthraquinone-benzacridone, 3 partsof sodium carbonate, 0.2 part of cuprous chloride and 70 parts ofnitro'oenzene are heated for 10 hours at 210 C. while stirring. Aftercooling, the condensation product is separated by filtering withsuction, and then washed with alcohol. The trianthrimide is thenextracted at the boil with hydrochloric acid of 2 percent. strength, themixture is filtered with suction, and the filter residue is washedneutral and dried. It is a dark violet powder which dissolves inconcentrated sulfuric acid with an olive-black coloration.

25 partsof aluminum chloride are introduced at 10- 70 C. into 50 partsof dry pyridine, while stirring. The mixture is heated up to 100 C., andat that temperature parts of the condensation product obtained asdescribed in the preceding paragraph are added. In the course of 45minutes the temperature is raised to 139-141 C. with the simultaneousdistillation of pyridine. The whole is then stirred for one hour at 140C. and the reaction product is poured into cold water. To the resultingsuspension there are added 120 parts of sodium hydroxide solution of 30percent strength and 25 parts of sodium hypochlorite solution containingpercent of active chlorine. The whole is heated to 90 C. while stirring,then filtered with suction, and the filter residue is washed neutral anddried. The dyestuff is a dark powder which dissolves in concentratedsulfuric acid with a dirty violet coloration, and dyes cotton from ayellowbrown vat fast black olive tints which are somewhat darker thanthose obtained with the dyestufi of Example 1.

Example 3 9.27 parts of 4-chloro-1:1-dianthrimide, 8.64 parts of 4 amino3-phenoxy-2:1(N)-1':2"(N)-anthraquinonebenzacridone, 0.2 part of copperacetate, 4 parts of sodium carbonate and 120 parts of nitrobenzene areheated for 8 hours at 210 C. while stirring. After cooling, thecondensation product is filtered oil with suction and then washed withalcohol. The dry anthrimide is then extracted at the boil withhydrochloric acid of 2 percent strength, the mixture is filtered withsuction, and the filter residue is washed neutral and dried. It is ablackviolet powder which dissolves in concentrated sulfuric acid with anolive coloration.

parts of aluminum chloride are introduced at 10- 90 C. into 50 parts ofpyridine while stirring. At 100 C. there are added to the resulting melt5 parts of the condensation product obtained as described in thepreceding paragraph. The temperature is raised to 139- 141" C. in thecourse of 45 minutes with the simultaneous distillation of pyridine. Thewhole is then stirred for one hour at 140 C., and the reaction productis poured into 4' Example 4 9.27 parts of 4-chloro-1:1-dianthrirnide,7.8 parts of 4.- amino 2: 1(N)-1':2'(N) anthraquinone naphthacridone 0.2part of copper acetate, 4 parts of sodium carbonate and 120 parts ofnitrobenzene are heated for 8 hours at 210 C., while stirring. Aftercooling, the condensation product is filtered off with suction, and thenWashed with alcohol. The trianthrimide is then extracted at the boilwith hydrochloric acid of 2 percent strength, filtered ofi with suction,and the filter residue is washed neutral and dried. It is a black powderwhich dissolves in concentrated sulfuric acid with an oliveyellowcoloration.

The resulting trianthrimide is carbazolized in the manner described inthe second paragraph of Example 3. The dyestutf is a dark powder whichdissolves in concentrated sulfuric acid with a black-violet colorationand dyes cotton from an orange-brown vat fast grey-olive tints.

Example 5 15.4 parts of 4-chloro-1:1-dianthrirnide, 13.8 parts of 4amino 5' phenyl 2:1(N)-1':2(N)-anthraquinonebenzacridone, 0.2 part ofcuprous chloride, 5 parts of sodium carbonate and 250 parts ofnitrobenzene are maintained for 8 hours at 210 C., while stirring. Aftercooling, the condensation product is filtered oil with suction and thenwashed with alcohol. The trianthrirriide is then extracted at the boilwith hydrochloric acid of 2 percent strength, filtered off with suction,and the filter residue is washed neutral and dried. It is a black powderwhich dissolves in concentrated sulfuric acid with a dark greencoloration.

The resulting trianthrimide is carbazolized in the manner described inthe second paragraph of Example 3. The dyestuif is a dark powder whichdissolves in concentrated sulfuric acid with a black-violet colorationand dyes cotton from an orange-brown vat fast olive tints.

The 4 amino 5- phenyl-2: l(N)'-l':2(N)-anthraquinone-benzacridone usedin the first paragraph of this example can be prepared, for example, asfollows:

33 parts of 1-chlbro-4-nitroanthraquinone-Z-carboxylic acid, 21 parts of4-arnino-1:1-diphenyl and 300 parts of ortho-dichlorobenzene are heatedfor 2 hours at 170- 180" C., while stirring. After cooling, the4-nitro-1- (para-phenyl)anilido-anthraquinone-Z-carboxyl-ic acid isfiltered off with suction, Washed with ether and dried.

40 parts of 4-nitro-1 (para-phenyl)-anilido-anthraqui- Inone-2-carboxylic acid, parts of benzoyl chloride and 250 parts ofortho-dichlorobenzene are stirred for 2 hours at C. After cooling thehandsome dark red crystals of the precipitated4-nitro-5-phenyl-2:1'(N)-1:2'(N)- .anthraquinone-benzacridone arefiltered off with suction, washed first with ortho-dichlorobenzene andthen with ether, and dried. The following values have been found byanalysis of a product obtained as described above:

Found Calculated The nitro group is reduced, for example, with sodiumsulfide in known manner. The resulting 4-amino-5-phenyl-Z:1(N)-1:2'(N)-anthraquinone benzacridone is a green-blue powderwhich dissolvesv in concentrated sulfuric acid with an orangecoloration.

Example 6 urn acetate, 0.5 part of magnesium oxide and 0.5 parts ofcuprous chloride are mixed in a finely divided state I p j 4 I v with100 parts of nitrobenze. The whole is heated and part of cuprouschloride are mixed in a finely powdered stirred while boiling well untilthe starting products have state with 80 parts -of nitrobenzene. Themixture is heatdisappeared. After cooling to 90 C., the mixture is filedand stirred while boiling well until the starting prodtered withsuction. The filter residue is purified by treat- 5 ucts havedisappeared. After cooling to 80 C., the mixment with nitrobenzene,alcohol, dilute hydrochloric acid ture is filtered with suction. Thefilter residue is puriand water, and then dried. The resulting powder isa fied by treatment with nitrobenzene, alcohol, dilute hytrianthrimideof the formula 6 parts of the latter tri-anthrimide are introduced at"drochloric acid and water, and is then dried. The powder 140 C. into athinly fluid homogeneous melt, which has so obtained is thetrianthrimide of the formula been prepared from a mixture of 60 parts ofsublimed aluminum chloride and 12 parts of dry powdered sodium 0chloride. The whole is stirred for about one hour at (3 150-155 C. Theliquid melt is then added to a solution of 90 parts of sodium hydroxidein 1360 parts of Water, NH- NH- the resulting suspension is vigorouslymixed for one hour at 70 C. and then filtered with suction. The washed V0: 0 0: O 0: 0

residue is added to a solution of 90 parts of sulfuric acid of 100percent strength in 270 parts of water. The resulting suspension isvigorously mixed for one hour at 70 C. and then filtered with suction.The residue is washed I 01 01 neutral and dried. The dyestutf soobtained is a dark powder which dissolves in concentrated sulfuric acidwith BY carbazohzmg the abova manthnmlde Wlth all alum! a violet browncoloration and dyes cotton from an olive- Chloride-Sodium Chloride meltin the er ebrown vat powerful olive tints having very good proper Scnbed111 Paragraph 2 of Example there i in d a i of fastness, dyestufr' whichdissolves in concentrated sulfuric acid By using as carbazolizing agent,instead f an lu i- With a violet-brown coloration and dyes cotton froman Hum ch10ride sodium chloride melt, a mixture f alumi- 40 orange brownvat powerful bluish olive'tints having very num chloride and acommercial mixture of 3- and 'ygood Properties of ne picoline a dyestufiis obtained having similar properties. Y Using for the r oIi tionaluminum chloride Instead of l-chloro-5-benzoylaminoanthraquinone theref and 'Y-P instead of aluminum C ido an may be used 1-chlo -o4-benzgylaminoanthraquinone in sodium chloride, there is obtained adyestuff having simithe manner described above for making atrianthn'mide, p p and the latter is carbazolized.

Example 8 Example 7 1 part of the carbazole obtained as described inExample 1 is vatted with the addition of 0.5 part of 10.1 parts of1-amino4-nitro-6:7-dianthraquinone, 11.3 Turkey rod oil in 100 parts ofWater y means of 2 Parts Parts of 4chloranthraquinone-Z;1(N)-1';2'(N)cben by volume of caustic sodasolution of 36 B. and 1 part acridone, 4 parts of anhydrous sodiumcarbonate, 1.5 Of i m hydrosulfite at about 50 C. I parts of magnesiumoxide and 0.6 part of copper car- The stock vat so prepared is added toa dyebath'conbonate are i d i a finely d d tat ith 200 sisting of 2000parts of water containing7 parts by volume parts of nitrobenzene. TheWhole is heated and stirred of caustic soda Solution of 6 and 6 Parts ofsodium while boiling well until the starting products havedishydrosulfite, and 160 p ts of e'tted cotton are entered appeared.After cooling, the mixture is filtered with suco the yebath at 40 C.After 15 minutes 10 parts tion at 50 C. The residueis purified bytreatment with of sodium chloride are added and dyeing is carried on fornitrobenzene, alcohol, dilute hydrochloric acid and water, one hourWhile slowly raising the temperature to 50 C. and is then dried. Thecotton is then squeezed, oxidizedin the air, rinsed, 13.2 parts of thefinely powdered nitro-dianthrimide acidified, soaped at the boil, againrinsed and dried. It obtained as described in the preceding paragraphare is dyedafast black-olive tint. mixed with 160 parts of nitrobenzene,the mixture is What is claimed is: heated to 110 C., and 4.5 parts ofhydrazine hydrate l. An'anthraquinonedyestutf of the formula (in theform of an ordinary commercial aqueous solution) are added in smallportions in the course of about 0 1% hours. The whole is stirred forabout 1 hour longer II at 100-110 C., and is then filtered with suction.The R filter residue is purified by treatment With nitrobenzene 79alcohol, dilute hydrochloric acid and Water, and is then dried.

6.3 parts of the lamino-dinathrimide so obtained, 2.9 parts ofl-chloranthraquinone, 1.4 parts of anhydrous sodium carbonate, 0.5 partof magnesium oxide and 0.5

2,837,52 .7 8 in which R represents ,a radical selected from the group3. The anthraquinonevat dyestufi of the formula consisting of theradicals corresponding to the formulae V 5 I ('11 (n) (0m E 4. Theanthraquinone vat dyestulf of the formula and in which n is a number ofat most two. 55 References Cfied 1n the file of thxs patent 2. The.anthraquinone vat dyestuff of the formula UNITED STATES PATENTS v 0 j Il,690,307 Mieg Nov. 6, 1928 y, 1,878,965 Mieg Sept. 20, 1932 f 2,036,663Weiland Apr. 7, 1936 1 NH 60 2,212,965 Wieners Aug. 27, 1940 2,315,537Miller Apr. 6, 1943 0 0 OTHER REFERENCES Synthetic Dyes, vol. II,Venkataraman, Academic Press, 65 N. Y. (1952), page 899.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Noa2,837,523 June 3, 1958 Maurice Grelat et ale It is hereby certified thaterror appears in the printed specification of the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 2, line 45, for "parts" read part line 5'7, for "introduce', readintroduced column 4, line 4, after "done" insert a comma; line '75, forparts" read m part column. 5, line 2, for

"nitrobenze" read nitrobenzene line '73, for 'amino dinathrimide' readamino=dianthrimide Signed and sealed this 2nd day of December 1958.,

(SEAL) Attest:

KARL Ho AXLINE ROBERT CwWATSON Commissioner of Patents Attesting Ofiicer

1. AN ANTHRAQUINONE DYESTUFF OF THE FORMULA